KR20180099709A - Hydrogen sulfide scavenging additive composition and method of use thereof - Google Patents

Abstract

The present invention relates to an additive composition for scavenging hydrogen sulphide in a hydrocarbon, said additive composition comprising (a) glyoxal and (b) at least one aliphatic tertiary amine or an oxide treated derivative thereof, or an aliphatic tertiary amine And a mixture of an oxide treated derivative thereof.
In one embodiment, the present invention is also directed to a method of scavenging hydrogen sulfide in a hydrocarbon, and in another embodiment, the present invention relates to a method of using the additive composition of the present invention for scavenging hydrogen sulfide in a hydrocarbon.
In another embodiment, the present invention relates to a composition for scavenging hydrogen sulphide in a hydrocarbon comprising (A) a hydrocarbon and (B) a hydrogen sulfide scavenging additive composition of the present invention.

Description

Hydrogen sulfide scavenging additive composition and method of use thereof

The present invention generally relates to improved hydrogen sulphide scavenging additive compositions and methods of use thereof.

In particular, the present invention relates to improved hydrogen sulfide scavenging compositions comprising (a) glyoxal and (b) at least one aliphatic tertiary amine or a combination of oxide treated derivatives of at least one aliphatic tertiary amine, An additive composition, a method of using the same, and a method of scavenging hydrogen sulfide from hydrocarbons containing a hydrocarbon stream.

The toxicity of hydrogen sulphide in a hydrocarbon or hydrocarbon stream is well known in the industry and requires significant cost and effort each year to reduce the content of hydrogen sulphide to a safe level.

In large-scale production facilities, it is generally more economical to install a regeneration system for treating the hydrogen sulfide stream. Typically, such a system employs a compound used in the absorber to contact the resulting fluid, optionally absorbing hydrogen sulphide and possibly other toxic substances such as carbon dioxide and mercaptans. Thereafter, the absorbing compound is regenerated and reused in the system. Typical hydrogen sulfide absorbing materials include alkanolamines, hindered amines, etc., i.e., nitrogen containing compounds. However, this approach is not economically feasible for the development phase of the field or in small production sites.

It is necessary to treat the sour hydrocarbon product as a non-regenerating scavenger for a development stage in the field where the regeneration system is not economical or at a small production site.

U.S. Patent No. 1,991,765 [US'765] discloses the use of aldehyde and hydrogen sulfide in aqueous solution. Thereafter, the use of aldehydes to remove or scaveng hydrogen sulfide has been reported in many patents. Aldehydes containing mainly formaldehyde or glyoxal combined with formaldehyde or other aldehydes combined with glyoxal or other aldehydes have been used as hydrogen sulfide scavenger / removing agents. In the formaldehyde type of reaction, the reaction produces a chemical complex known as formthional (e.g., trithiane).

Non-regenerative scavengers for the removal of hydrogen sulfide from small plants include four groups: aldehyde based, metal oxide based, caustic based, and other processes.

In the removal of hydrogen sulphide by non-regenerating compounds, the scavenger reacts with hydrogen sulfide to form compounds that can be removed from the non-toxic compounds or hydrocarbons.

U.S. Patent No. 4,680,127 [US'127] reported that hydrogen sulfide is scavenged as a result using glyoxal, or glyoxal combined with small amounts of other aldehydes.

However, a major problem with this method is that it is stable only at alkaline pH of about pH 9 and leads to the formation of a water-soluble product that degrades at an acidity of about pH 4.5 to 5.5.

The solution to the above problem of US'127 was provided by US Patent No. 5,085,842 [US'842] which reported the use of a very high amount of glyoxal of at least 15 wt%, preferably 25 to 45 wt%.

The main problem with this solution is that glyoxal should be used in very high amounts, which also makes the process very uneconomical. A further problem with this method is that it is liable to deposit on the container as a result, which results in contamination, thereby resulting in a product which means that additional antifouling additives may be required. Therefore, this method is not economical for the inventors of the present invention, nor is it industrially easy or convenient.

In addition, U.S. Patent No. 6,666,975 [US '975] reported the use of glyoxal for the purpose of providing a method for reducing the release of hydrogen sulfide odors, the products formed being water soluble and non-volatile. US 975 is not intended to overcome the problem of contamination in hydrocarbon treatment which may be caused by the water insoluble product formed by the use of the high amount of glyoxal reported in US'842, , And b) the problem of scavenging hydrogen sulphide without encountering the problem of degradation of the product which can be decomposed at a soluble pH but which can be generated by using the method of US ' To avoid the handling problem of glyoxal without disclosing or teaching how to achieve it. It does not even discuss US'842 and US'127 in US'975.

Requirement of invention:

Therefore,

Comprising a substantially reduced amount of glyoxal,

It is also required in a substantially reduced amount,

Is suitable for scavenging sulfur-containing compounds comprising hydrogen sulphide and mercaptan, especially hydrogen sulphide, in a hydrocarbon or hydrocarbon stream,

As an improved additive composition that overcomes one or more of the above-mentioned problems of the prior art,

Wherein the additive composition can increase the hydrogen sulfide scavenging efficiency of prior art compositions composed of glyoxalane, and

Wherein the additive composition is capable of scavenging sulfur-containing compounds at room temperature as well as at higher temperatures,

There is still a need for improved additive compositions.

Accordingly, the present invention provides an improved additive composition for scavenging sulfur-containing compounds comprising hydrogen sulfide and mercaptan, especially hydrogen sulfide, in a hydrocarbon or hydrocarbon stream without causing any problems, ≪ / RTI > wherein the additive composition comprises at least

Comprising a substantially reduced amount of glyoxal,

It is also required in a substantially reduced amount,

Is suitable for scavenging sulfur-containing compounds comprising hydrogen sulphide and mercaptan, especially hydrogen sulphide, in a hydrocarbon or hydrocarbon stream,

As an improved additive composition that overcomes one or more of the above-mentioned problems of the prior art,

Wherein the additive composition can increase the hydrogen sulfide scavenging efficiency of prior art compositions composed of glyoxalane, and

Wherein the additive composition is capable of scavenging sulfur containing compounds at room temperature as well as at higher temperatures.

Object of the invention:

Thus, a primary objective of the present invention is to provide a process for scavenging sulfur containing compounds comprising hydrogen sulfide (H ₂ S) and mercaptan, especially hydrogen sulfide (H ₂ S), in a hydrocarbon or hydrocarbon stream, To provide an improved additive composition that reduces one or more of the problems, wherein the additive composition comprises

Comprising a substantially reduced amount of glyoxal,

It is also required in a substantially reduced amount,

Is suitable for scavenging sulfur-containing compounds comprising hydrogen sulphide and mercaptan, especially hydrogen sulphide, in a hydrocarbon or hydrocarbon stream,

As an improved additive composition that overcomes one or more of the above-mentioned problems of the prior art,

Wherein the additive composition can increase the hydrogen sulfide scavenging efficiency of prior art compositions composed of glyoxalane, and

Wherein the additive composition is capable of scavenging sulfur containing compounds at room temperature as well as at higher temperatures.

It is also an object of the present invention to provide a method of scavenging hydrogen sulphide in a sulfur containing compound, especially a hydrocarbon or hydrocarbon stream comprising hydrogen sulfide and mercaptan, by using the presently provided additive composition of the present invention comprising a substantially reduced amount of glyoxal Which is also used in a substantially reduced amount to scavenge the sulfur containing compound and the additive composition is used to increase the hydrogen sulfide scavenging efficiency of prior art compositions composed of glyoxalane Can be; Wherein the additive composition scavenges sulfur-containing compounds at even higher temperatures as well as at room temperature.

It is also an object of the present invention to provide a method of using the additive composition of the present invention for scavenging hydrogen sulphide in a sulfur containing compound, especially a hydrocarbon or hydrocarbon stream comprising hydrogen sulfide and mercaptan, A substantially reduced amount of glyoxal, thereby making said composition and its use economically, industrially feasible and convenient.

Other objects and advantages of the invention will become more apparent from the following detailed description, taken in conjunction with the embodiments, which are not intended to limit the scope of the invention.

With the aim to overcome the above-mentioned problems of the prior art and to achieve the objects of the present invention described above, the inventors have found that hydrocarbons comprising sulfur-containing compounds containing hydrogen sulfide and / or mercaptans comprise at least the following combinations Sulfur compounds containing hydrogen sulfide are scavenged or removed when treated with an additive composition:

(a) glyoxal; And

(b) an oxide treated derivative of at least one aliphatic tertiary amine or at least one aliphatic tertiary amine, or a mixture thereof.

In order to overcome the problems of the prior art mentioned above and to achieve the object of the present invention mentioned above, the present inventors have found that the additive composition of the present invention contains a substantially reduced amount of glyoxal and / It has been found that scavenging of sulfur-containing compounds is also achieved when used in reduced amounts.

The inventors of the present invention have found that, for the purpose of overcoming the problems of the above-mentioned prior art and achieving the object of the present invention mentioned above, the additive composition of the present invention has a surprising and unexpected effect (synergistic effect) as well as at higher temperatures.

Thus, in a key implementation, the present invention is directed to an additive composition for scavenging hydrogen sulphide in a hydrocarbon, said additive composition comprising at least

(a) glyoxal; And

(b) an oxide-treated derivative of at least one aliphatic tertiary amine or at least one aliphatic tertiary amine, or a mixture thereof

. ≪ / RTI >

Thus, in another embodiment, the present invention is directed to a method of scavenging hydrogen sulphide in a hydrocarbon, said method comprising contacting at least a hydrocarbon containing a sulfur-

(a) glyoxal; And

(b) an oxide-treated derivative of at least one aliphatic tertiary amine or at least one aliphatic tertiary amine, or a mixture thereof

To < / RTI > the additive composition of the present invention.

Thus, in another embodiment, the present invention provides a process for scavenging hydrogen sulphide from hydrocarbons,

(a) glyoxal; And

(b) an oxide-treated derivative of at least one aliphatic tertiary amine or at least one aliphatic tertiary amine, or a mixture thereof

Wherein the method comprises treating a hydrocarbon containing a sulfur containing compound comprising hydrogen sulfide with an additive composition of the present invention.

Thus, in another embodiment, the present invention relates to a composition for scavenging hydrogen sulphide in a hydrocarbon,

(A) a hydrocarbon including a sulfur-containing compound; And

(B) Hydrogen sulfide scavenging additive composition

/ RTI >

Wherein the hydrogen sulfide scavenging additive composition comprises at least

(a) glyoxal; And

(b) an oxide-treated derivative of at least one aliphatic tertiary amine or at least one aliphatic tertiary amine, or a mixture thereof

, ≪ / RTI >

Wherein the aliphatic tertiary amine or an oxide treated derivative of the aliphatic tertiary amine is as described herein.

According to one preferred embodiment of the invention, the aliphatic tertiary amine comprises tri-isopropanolamine (TIPA).

According to one preferred embodiment of the present invention, the aliphatic tertiary amine comprises N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylene-diamine (THEED).

According to one preferred embodiment of the present invention, the aliphatic tertiary amine comprises N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylene-diamine (Quadrol).

According to one preferred embodiment of the present invention, the oxide treated derivative of an aliphatic tertiary amine comprises an ethylene oxide (EO) derivative of tri-isopropanolamine (EO-TIPA).

According to one preferred embodiment of the present invention, the oxide treated derivative of an aliphatic tertiary amine comprises a propylene oxide (PO) derivative of tri-isopropanolamine (PO-TIPA).

According to one of the preferred embodiments of the present invention, the oxide treated derivative of an aliphatic tertiary amine comprises an ethylene oxide (EO) derivative (EO-TEA) of triethanolamine.

According to one preferred embodiment of the present invention, the oxide treated derivative of an aliphatic tertiary amine comprises a propylene oxide (PO) derivative (PO-TEA) of triethanolamine.

According to one preferred embodiment of the present invention, the aliphatic tertiary amine is selected from the group consisting of tri-isopropanolamine (TIPA), N, N, N ', N'-tetrakis (2- hydroxyethyl) ethylene- diamine N ', N'-tetrakis (2-hydroxypropyl) ethylene-diamine (Quadrol®), or mixtures thereof.

According to one of the preferred embodiments of the invention, the oxide treated derivative of an aliphatic tertiary amine is selected from the group consisting of ethylene oxide (EO) derivatives of triisopropanolamine (EO-TIPA), propylene oxide (PO) derivatives of triisopropanolamine (EO-TEA) of triethanolamine, propylene oxide (PO) derivative (PO-TEA) of triethanolamine, or a mixture thereof.

The present inventors have found that, in order to overcome the above-mentioned problems of the prior art and to achieve the object of the present invention mentioned above, the present inventors have found that when the composition contains triethanolamine (TEA), monoethanolamine (MEA), diethanolamine In the case of containing tetraethylenepentaamine (TEPA), it has been found that the hydrogen sulfide scavenging efficiency of the prior art additives increases, but does not increase to an actual economic level.

Thus, in one embodiment of the invention, the additive composition of the present invention does not comprise triethanolamine (TEA), monoethanolamine (MEA), diethanolamine (DEA) and tetraethylene pentaamine (TEPA).

According to one of the preferred embodiments of the present invention, the hydrocarbon comprises a hydrocarbon stream comprising crude oil, fuel oil, sour gas, asphalt and purified product contained in storage tanks, vessels and pipelines.

According to one preferred embodiment of the present invention, the hydrogen sulfide containing compound comprises a sulfur containing compound, or a mercaptan or a mixture thereof.

According to another embodiment, the present invention relates to a method of scavenging hydrogen sulfide in a hydrocarbon comprising a sulfur containing compound, the method comprising contacting the hydrogen sulfide scavenging additive composition of the present invention described herein with a hydrocarbon .

According to another embodiment, the present invention is directed to a method of using a hydrogen sulfide scavenging additive composition for scavenging hydrogen sulfide in a hydrocarbon comprising a sulfur containing compound, And adding the hydrogen sulfide scavenging additive composition of the invention.

According to one of the preferred embodiments of the present invention, the hydrocarbons include, but are not limited to, crude oil, fuel oil, sour gas, asphalt, and hydrocarbon streams containing or containing purified products contained in storage tanks, vessels and pipelines ≪ / RTI >

According to one preferred embodiment of the invention, the hydrogen sulphide comprises or contains a sulfur-containing compound and a mercaptan.

Thus, according to one of the preferred embodiments of the present invention, in performing the scavenging method of the present invention or the method of using the additive composition of the present invention for scavenging hydrogen sulfide in a hydrocarbon or hydrocarbon stream, the scavenging additive composition Is added at a concentration sufficient to substantially scaveng a hydrocarbon or gas stream or hydrocarbon stream to hydrogen sulphide therein.

According to one of the preferred embodiments of the present invention, the scavenging additive composition is used in a method of using the additive composition of the present invention and in a method of scavenging a hydrogen sulfide-containing compound in a hydrocarbon or hydrocarbon stream by using the additive composition of the present invention By weight of the hydrocarbon or hydrocarbon stream, in various amounts of from about 0.1 to about 4000 ppm, preferably from about 1 to about 3000 ppm, and more preferably from about 5 to about 2000 ppm.

According to one of the preferred embodiments of the invention, a mixture of the components of the present invention can be obtained by mixing component (a) and component (b) of the present invention in any weight (or mole) ratio.

According to one of the preferred embodiments of the present invention, hydrogen sulfide scavenging can be carried out at an appropriate temperature.

The present inventors have also found that when the additive composition of the present invention is used, it scavens the sulfur-containing compound in the hydrocarbon or hydrocarbon stream much more quickly than the additive consisting of glyoxalane.

The additive composition of the present invention comprising the same amount of additive composition consisting of glyoxal (alone) and an oxide treated derivative of glyoxal and an aliphatic tertiary amine or aliphatic tertiary amine, or a mixture thereof, was used for 2 hours In the case of scavenging sulfur-containing compounds in hydrocarbons, the percent efficiency of scavenging sulfur-containing compounds with the additive compositions of the present invention was found to be substantially higher than that of glyoxal additives, Confirming that the composition acts at a higher rate to scavenge sulfur-containing compounds in hydrocarbons or hydrocarbon streams than additives composed of glyoxal.

From the foregoing description and the following supported embodiments, reference has been made to this specification, which can be concluded as follows:

The efficiency of glyoxal for the hydrogen sulfide scavenging is determined by the oxidation of the aliphatic tertiary amine or aliphatic tertiary amine of the present invention, or a mixture thereof (also referred to as "Co-Additive" Is substantially improved at both the room temperature and the high temperature (e.g., at 80 ° C);

The efficiency improvement of glyoxal for hydrogen sulfide scavenging is substantially higher when the co-additive of the present invention is added at high temperature (e.g., 80 DEG C) compared to at room temperature;

As noted above, the major problem with using glyoxal in larger amounts is that it makes the process very uneconomical, and makes it industrially impractical and inconvenient. In addition, the use of higher amounts of glyoxal results in water-insoluble products, which are prone to fouling because they are more likely to precipitate in containers. Thus, as the amount of glyoxal required in the additive composition of the present invention is substantially reduced, the problem associated with greater amounts of glyoxal is overcome.

According to one of the preferred embodiments of the present invention, the scavenging additive composition of the present invention is injected into flow lines in the field development stage or in a small production site, or in the case of mass production equipment, A gas containing hydrogen sulfide can be passed through the absorber into which the cavitation additive composition is injected.

The scavenging additive composition and method of the present invention scavenges hydrogen sulphide and mercaptans from a hydrocarbon or hydrocarbon stream comprising crude oil, fuel oil, sour gas, asphalt, and purified products contained in storage tanks, vessels, and pipelines .

According to one embodiment of the present invention, the additive composition can be used to scavenge sulfur containing compounds, including hydrogen sulfide and mercaptans, from crude oil when passed through a desalinization or treated with wash water in a crude processing system.

According to one embodiment of the present invention, any active prior art additive glyoxal can be used in the present invention.

The molecular weight or average molecular weight of the additive can be measured by Daltons by any known technique, for example, gel permeation chromatography (GPC).

Abbreviations used herein have the following meanings:

TIPA is Tri-IsoPropanolAmine and an aliphatic tertiary amine. The TIPA used in this experiment is 99% pure (active);

TheED is an aliphatic tertiary amine and its chemical name is N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylene-diamine or alternatively (2,2', 2 " '' '- (1,2-ethanediyl dinitrile) tetraethanol);

Quadrol® is an aliphatic tertiary amine and its chemical name is N, N, N ', N' tetrakis (2-hydroxypropyl) ethylene-diamine.

EO-TIPA or ethoxylated TIPA is an ethylene oxide (EO) derivative of TIPA, which can be obtained by reacting one mole of TIPA with at least one mole of ethylene oxide (EO). For example, ethoxylated TIPA can be obtained by reacting 1 mole of TIPA with 1 to 50 moles of ethylene oxide (EO). EO-TIPA can be prepared using ethylene oxide of various molecular weights to obtain desired additives of various molecular weights. For example, the additive may have a variety of molecular weights ranging from 400-1200 daltons, preferably 700-800 daltons.

PO-TIPA or propoxylated TIPA is a propylene oxide (PO) derivative of TIPA that can be obtained by reacting 1 mole of TIPA with at least 1 mole of propylene oxide (PO). For example, propoxylated TIPA can be obtained by reacting 1 mole of TIPA with 1 to 50 moles of propylene oxide (PO). PO-TIPA may be prepared using propylene oxide of various molecular weights to obtain desired additives of various molecular weights. For example, the additive may have a variety of molecular weights ranging from 300 to 1500 daltons, preferably 300 to 750 daltons, preferably 1100 to 1300 daltons, and may be used.

TEA is triethanolamine;

EO-TEA or ethoxylated TEA is an ethylene oxide (EO) derivative of TEA that can be obtained by reacting 1 mole of TEA with at least one mole of ethylene oxide (EO). For example, ethoxylated TEA can be obtained by reacting 1 mole of TEA with 1 to 50 moles of ethylene oxide (EO). EO-TEA can be prepared using ethylene oxide of various molecular weights to obtain desired additives of various molecular weights. For example, the additive may have a molecular weight of from 400 to 1300 Daltons, preferably from 900 to 1300 Daltons, preferably from 1000 to 1250 Daltons, and may be used.

PO-TEA or propoxylated TEA is a propylene oxide (PO) derivative of TEA which can be obtained by reacting 1 mole of TEA with at least one mole of propylene oxide (PO). For example, propoxylated TEA can be obtained by reacting 1 mole of TEA with 1 to 50 moles of propylene oxide (PO). PO-TEA can be prepared using propylene oxide having various molecular weights to obtain desired additives having various molecular weights. For example, the additive may have a molecular weight of 800 to 2400 Daltons, preferably 1000 to 2200 Daltons, preferably 1000 to 2150 Daltons, and may be used.

The MEA is monoethanolamine,

DEA is DiEthanol Amine;

TEPA is TetraEthylene PentaAmine.

The present invention is not intended to be limited to the scope of the present invention, but is described using the following embodiments which are included to illustrate the advantages of the invention and the best mode for carrying it out. The following examples also demonstrate the surprising effects of the scavenging additive compositions of the present invention.

Example:

The H ₂ S was purged at 100ml kerosene until at 2000ppm - [I Blank] The vapor concentration of the H ₂ S ball samples. To the resulting solution was added a dose of the prior art additive and the additive composition of the present invention as given in the table below at a shake time of 1 min and the H ₂ S scavenging ability at room temperature (RT) and 80 Lt; 0 > C. The results are shown in Tables I to VI below.

In this example, the glyoxal used is 40% active.

The experimental results of Tables I to IV show that at least (a) glyoxal and (b) a combination of aliphatic tertiary amines wherein the aliphatic tertiary amine is present in the present invention comprising TIPA, EO-TIPA or PO- Is synergistic and shows surprising and unexpected effects compared to prior art compositions consisting of glyoxalans.

The H2S scavenging efficiency of the composition consisting of glyoxal

[Prior Art Composition]

First, the experimental data in Table V confirms that the H ₂ S scavenging efficiency of prior art compositions deteriorates at high temperatures.

Secondly, prior art compositions composed of glyoxal (bare) do not exhibit H ₂ S scavenging efficiency at high temperatures because only 20% H ₂ S scavenging could be achieved at a dose of 1000 ppm to be. At lower temperatures, only 70% H ₂ S scavenging could be achieved at substantially higher doses of 1000 ppm.

The H2S scavenging efficiency of a composition comprising TIPA

[Additive of the invention, but taken alone]

Since only 5% H ₂ S scavenging could be achieved with a dose of 25 ppm, the inventive additive TIPA alone does not show the efficiency of scavenging H ₂ S. Thus, the additive itself (i.e., when taken alone) is not an H ₂ S scavenging additive.

The H2S scavenging efficiency of a composition comprising glyoxal and monoethanolamine (MEA)

[Comparative composition]

The comparison composition comprising glyoxal and MEA showed that the H ₂ S scavenging efficiency of glyoxal was only 20% to 40% at high temperature and 60% to 65% at low temperature by adding 50 ppm of MEA to 500 ppm of glyoxal, , It does not show an improvement in the H ₂ S scavenging efficiency of the prior art compositions composed of glyoxal (alone).

The H ₂ S scavenging efficiency of a composition comprising glyoxal (40%) and diethanolamine (DEA)

[Comparative composition]

The comparative compositions comprising glyoxal and DEA also showed no improvement in the H ₂ S scavenging efficiency of the prior art compositions composed of glyoxal alone because of the addition of 50 ppm DEA to 500 ppm glyoxal, The H ₂ S scavenging efficiency of oxal was increased from 20% to 25% at a much lower temperature and at a much lower temperature, since this did not show any improvement, ie it remained at 60%.

The H ₂ S scavenging efficiency of a composition comprising glyoxal (40%) and triethanolamine (TEA)

[Comparative composition]

The comparative composition comprising glyoxal and TEA also showed no improvement in the H ₂ S scavenging efficiency of the prior art compositions consisting of glyoxal alone because of the addition of 50 ppm TEA to 500 ppm glyoxal, The H ₂ S scavenging efficiency of oxal was increased from 20% to 25% at very high and low temperatures, which is a very slight improvement of 60% to 65%.

The H ₂ S scavenging efficiency of a composition comprising glyoxal and tetraethylenepentamine (TEPA)

[Comparative composition]

The comparative composition comprising glyoxal and TEA also showed no improvement in the H ₂ S scavenging efficiency of the prior art compositions consisting of glyoxal alone because even with the addition of 50 ppm TEPA to 500 ppm glyoxal, The H ₂ S scavenging efficiency of oxal was increased from 20% to 40% at very high and low temperatures, which was a very slight improvement of 60% to 65%.

The H ₂ S scavenging efficiency of a composition comprising glyoxal and TIPA

[Invention composition]

The combination of the present invention comprising glyoxal and TIPA is characterized in that when only 25 or 50 ppm of TPA is added to 500 ppm of glyoxal at high temperature, the H ₂ S scavenging efficiency of the composition consisting of glyoxal Gt; 20% < / RTI > to 65%, or 70%, relative to the amount of < RTI ID = 0.0 > Likewise, the synergistic effect of the present invention can be observed at low temperatures, where the H ₂ S scavenging efficiency of glyoxal is only 60% to 92% or 95% when 50 or 100 ppm of TIPA is added to 500 ppm of glyoxal %.

H2S scavenging efficiency of a composition comprising glyoxal and THEED

[Invention composition]

The combination of the present invention comprising glyoxal and THEED can also be used to reduce the H ₂ S scavenging efficiency of prior art compositions to 500 ppm when only 25 or 50 ppm of THEED is added to 500 ppm of glyoxal at low temperature as well as at low temperature With increasing TIPA from 60% to 90% or 95% when adding only 25 or 50 ppm of TIPA to glyoxal at 20% to 70% or 75% at room temperature and 500 ppm at room temperature, surprisingly and unexpectedly .

H2S scavenging efficiency of a composition comprising glyoxal and Quadrol®

[Invention composition]

The combination of the present invention comprising glyoxal and quadrol can be used to increase the H ₂ S scavenging efficiency of the composition consisting of glyoxal (alone) to 500 ppm when a quadruple of only 50 mmp at high temperature is added to 500 ppm of glyoxal Gt; 20% < / RTI > to 55% relative to the amount of < RTI ID = 0.0 > Similarly, the synergistic effect of the present invention also appeared at low temperatures, where the H ₂ S scavenging efficiency of glyoxal was improved from 60% to 80% when 50 ppm of quadrol was added to 500 ppm of glyoxal .

The experimental data in Table VI confirms that the H ₂ S scavenging efficiency of glyoxal (and TEA) is improved by the addition of EO-TEA (for ethoxylation of TEA).

Also, the experimental data in Table VI confirms that the addition of PO-TEA (or propoxylation of TEA) improves the H ₂ S scavenging efficiency of glyoxal (and TEA).

The above example confirms the synergistic effect, that is, the surprising and unexpected effect of the present invention over the prior art.

Thus, the experiment confirms that glyoxal H ₂ S can be scavenged. However, when using the compositions of the present invention comprising glyoxal and an oxide treated derivative of at least one aliphatic tertiary amine or at least one aliphatic tertiary amine, or a combination of these, the H ₂ S scavenging efficiency of glyoxal Surprisingly and unexpectedly, substantially increases, confirming the synergistic effect of the scavenging additive composition of the present invention.

The experimental results confirm the surprising and unexpected technical effects and advantages of the presently provided hydrogen sulfide scavenging additive composition, and the ascending characteristics.

This discovery also confirms that the compositions of the present invention have technical and surprising effects over prior art and comparative additives and compositions.

While the invention has been described with the aid of the above-described embodiments, it is to be noted that this is illustrative rather than limiting the scope of the invention.

Also, as the amount of prior art additives (i.e., glyoxal) is substantially reduced to achieve the desired scavenging efficiency, the compositions of the present invention are more economical and environmentally friendly.

It should be noted that the term "about " as used herein is not intended to extend the scope of the claimed invention but merely incorporated to encompass acceptable experimental errors in the technical field of the present invention.

Claims (16)

A hydrogen sulfide scavenging additive composition for scavenging hydrogen sulfide from hydrocarbons comprising sulfur containing compounds, wherein the additive composition comprises at least
(a) glyoxal; And
(b) an oxide-treated derivative of at least one aliphatic tertiary amine or at least one aliphatic tertiary amine, or a mixture thereof
≪ / RTI >
The method according to claim 1,
Wherein the aliphatic tertiary amine comprises tri-isopropanolamine (TIPA).
3. The method according to claim 1 or 2,
Wherein the aliphatic tertiary amine comprises N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylene-diamine (THEED).
4. The method according to any one of claims 1 to 3,
An additive composition wherein the aliphatic tertiary amine comprises N, N, N ', N' tetrakis (2-hydroxypropyl) ethylene-diamine (Quadrol).
5. The method according to any one of claims 1 to 4,
An oxide composition of an aliphatic tertiary amine comprising an ethylene oxide (EO) derivative of tri-isopropanolamine (EO-TIPA).
6. The method according to any one of claims 1 to 5,
Wherein the oxide treated derivative of an aliphatic tertiary amine comprises a propylene oxide (PO) derivative of tri-isopropanolamine (PO-TIPA).
7. The method according to any one of claims 1 to 6,
An oxide composition of an aliphatic tertiary amine comprising an ethylene oxide (EO) derivative of triethanolamine (EO-TEA).
8. The method according to any one of claims 1 to 7,
Wherein the oxide treated derivative of an aliphatic tertiary amine comprises a propylene oxide (PO) derivative of triethanolamine (PO-TEA).
9. The method according to any one of claims 1 to 8,
The aliphatic tertiary amine can be selected from the group consisting of tri-isopropanolamine (TIPA), N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylene- diamine (THEED) (2-hydroxypropyl) ethylene-diamine (Quadrol), or mixtures thereof.
10. The method according to any one of claims 1 to 9,
Oxidated derivatives of aliphatic tertiary amines include ethylene oxide (EO) derivatives of tri-isopropanolamine (EO-TIPA), propylene oxide (PO) derivatives of triisopropanolamine (PO-TIPA), triethanolamine ethylene oxide EO) derivative (EO-TEA), a propylene oxide (PO) derivative of triethanolamine (PO-TEA), or a mixture thereof.
11. The method according to any one of claims 1 to 10,
Wherein the composition does not comprise triethanolamine (TEA), monoethanolamine (MEA), diethanolamine (DEA), and tetraethylene pentaamine (TEPA).
12. The method according to any one of claims 1 to 11,
The hydrocarbon comprises a hydrocarbon stream comprising crude oil, fuel oil, sour gas, asphalt, and refined products contained in a storage tank, vessel and pipeline.
13. The method according to any one of claims 1 to 12,
Wherein the hydrogen sulfide-containing compound comprises a sulfur-containing compound, or a mercaptan, or a mixture thereof.
A composition for scavenging hydrogen sulfide,
The composition
(a) a hydrocarbon comprising a sulfur-containing compound; And
(b) a hydrogen sulfide scavenging additive composition
/ RTI >
Wherein the hydrogen sulfide scavenging additive composition comprises at least
(A) glyoxal; And
(B) at least one aliphatic tertiary amine or an oxide treated derivative thereof, or a mixture of an aliphatic tertiary amine and an oxide treated derivative thereof
, ≪ / RTI >
Wherein said aliphatic tertiary amine or an oxide treated derivative thereof is as claimed in any one of claims 1 to 13.
A method for scavenging hydrogen sulphide from hydrocarbons comprising sulfur containing compounds,
The method comprises contacting a hydrocarbon with a hydrogen sulfide scavenging additive composition, wherein the hydrogen sulfide scavenging additive composition is as claimed in any one of claims 1 to 13.
A method of using a hydrogen sulfide scavenging additive composition for scavenging hydrogen sulfide from hydrocarbons comprising sulfur containing compounds,
Wherein the method comprises adding a hydrogen sulfide scavenging additive composition as claimed in any one of claims 1 to 13 to the hydrocarbon.